CN102713010A - Hydrogen generation device - Google Patents
Hydrogen generation device Download PDFInfo
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- CN102713010A CN102713010A CN2011800065068A CN201180006506A CN102713010A CN 102713010 A CN102713010 A CN 102713010A CN 2011800065068 A CN2011800065068 A CN 2011800065068A CN 201180006506 A CN201180006506 A CN 201180006506A CN 102713010 A CN102713010 A CN 102713010A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
- C25B1/55—Photoelectrolysis
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/066—Integration with other chemical processes with fuel cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
Disclosed is a hydrogen generation device (100) comprising: a transparent substrate (1); a photocatalyst electrode (4) arranged on the transparent substrate (1) and composed of a transparent conductive layer (2) and a photocatalyst layer (3); a counter electrode (8) electrically connected to the transparent conductive layer (2); an electrolytic solution layer arranged between the photocatalyst electrode (3) and the counter electrode (8) and containing water; a separator (6) for dividing the electrolytic solution layer into a first electrolytic solution layer (5) that is in contact with the photocatalyst electrode (4) and a second electrolytic solution layer (7) that is in contact with the counter electrode (8); a first gas outlet (14) for removing a gas generated in the inside of the first electrolytic solution layer (5); and a second gas outlet (15) for removing a gas generated in the inside of the second electrolytic solution layer (7). The photocatalyst electrode (4) and the counter electrode (8) are so arranged that the surface of the photocatalyst layer (3) and the surface of the counter electrode (8) face each other. The separator (6) is so adapted that an electrolyte contained in the electrolytic solution layer can permeate through the separator (6) and a hydrogen gas and an oxygen gas contained in the electrolytic solution layer cannot permeate through the separator (6).
Description
Technical field
The present invention relates to use up through making that to split water into hydrogen and oxygen be the hydrogen generation apparatus of purpose to obtain hydrogen.
Background technology
At present, bring into play as photocatalyst function semiconductor material utilize that method is known to be had through to said semiconductor material irradiates light, water of decomposition extracts hydrogen thus, perhaps extracts the method (for example, with reference to patent documentation 1 and 2) of electric energy.
In patent documentation 1, disclose water decomposition with structure that photocatalyst is overlapped with solar cell with semiconductor photoelectrode with used this water decomposition to use system with the water decomposition of semiconductor photoelectrode.This semiconductor photoelectrode from the sensitive surface side comprise photocatalyst film, nesa coating in order, the transparency carrier, nesa coating, electrolyte solution, the titanium oxide layer that has supported pigment, metal substrate, the hydrogen that possess the electrode that is used for table is electrically connected between the back side generates and uses catalyst layer.In patent documentation 1, disclose through this semiconductor photoelectrode being shone sunshine the content of water decomposition with extraction hydrogen and oxygen.Particularly, put down in writing, used the film of from the group that constitutes by titanium oxide, Tungsten oxide 99.999 and red oxide of iron, selecting that material constituted as photocatalyst film.
The regeneration type photoelectrochemical cell that possesses as many crystallinity MOS of photocatalyst is disclosed in patent documentation 2.In patent documentation 2, disclosing many crystallinity MOS does not corrode and has in the scope of visible spectrum the photoelectrochemical cell of the electric energy yield that (more detailed, in the spectrographic scope of solar ray) improved and make usage.
TP formerly
Patent documentation
Patent documentation 1: TOHKEMY 2006-265697 communique
Patent documentation 2: No. 2664194 communique of Japanese Patent
Summary of the invention
Yet; With regard to patent documentation 1 disclosed water decomposition with regard to system; Water decomposition with semiconductor photoelectrode in, generate the photocatalyst film surface at position and the hydrogen generation that generates the position as hydrogen with being separated by semiconductor photoelectrode self between the catalyst layer surface as oxygen.Therefore, proton only moves through the gap that is provided with in the bottom of semiconductor photoelectrode, can't produce hydrogen fully and generate and neededly generate mobile with the proton of catalyst layer side from photocatalyst film side direction hydrogen.Consequently,, hydrogen is absorbed in the rate of diffusion state of a control of proton near generating with catalyst layer, the progress of the formation reaction of hydrogen and oxygen along with irradiates light, and reaction efficiency reduces.And, generate with hydrogen and not have to be provided with the blended mechanism that prevents gas between the position owing to generate the position, so the hydrogen of generation mixes each other with oxygen and is difficult to Separation and Recovery at oxygen.
Therefore; The present invention proposes in view of above-mentioned existing problem points; Its problem is to provide a kind of hydrogen generation apparatus to extract the equipment of hydrogen as the decomposition reaction that utilizes the caused water of photocatalyst; Thereby the situation that the efficient that can suppress the formation reaction of hydrogen and oxygen reduces along with the progress of reaction improves the efficient of hydrogen formation reaction, and then easily reclaims the hydrogen that is generated.
Hydrogen generation apparatus provided by the invention possesses:
Transparency carrier;
The photocatalyst electrode, it is formed by the photocatalyst layer that is configured in the transparency conducting layer on the said transparency carrier and be configured on the said transparency conducting layer;
Antipole, it is electrically connected with said transparency conducting layer;
Electrolyte layer, it is arranged between said photocatalyst electrode and the said antipole and contains water;
Partition member, it is separated into first electrolyte layer that joins with said photocatalyst electrode and second electrolyte layer that joins with said antipole with said electrolyte layer;
The first gas conveying end, it is connected with said first electrolyte layer, is used to take out oxygen or the hydrogen that produces in the inside of said first electrolyte layer;
The second gas conveying end, it is connected with said second electrolyte layer, is used to take out hydrogen or the oxygen that produces in the inside of said second electrolyte layer,
Said photocatalyst electrode disposes with the mode that the surface of said antipole is faced mutually with the surface of said antipole with said photocatalyst layer,
Said partition member can make the ionogen in the said electrolyte layer see through and the hydrogen and the oxygen that suppress in the said electrolyte layer see through.
The invention effect
According to hydrogen generation apparatus of the present invention, it is near that the distance on the surface of photocatalyst layer and the surface of antipole becomes on whole.Thereby, produce proton fully and reach diffusion to the surface of the photocatalyst layer that generates the position as hydrogen or the moving of surface of antipole.Consequently, the efficient of hydrogen formation reaction is improved.And electrolyte layer separates into first electrolyte layer that joins with photocatalyst layer and second electrolyte layer that joins with antipole by the hydrogen that can make ionogen in the electrolyte layer see through and be suppressed to produce in the electrolyte layer and the partition member that sees through of oxygen.Thereby, can easily be separated in oxygen (or hydrogen) that produces on the photocatalyst laminar surface and the hydrogen (or oxygen) that on the antipole surface, produces, the recovery of the feasible hydrogen that generates is easy.
Description of drawings
Fig. 1 is the sketch of the structure of the hydrogen generation apparatus that relates to of expression embodiment 1 of the present invention.
Fig. 2 is the figure that the viewpoint from the direction of illumination of light is illustrated in first thrust that is provided with as the fixed support member on the hydrogen generation apparatus that embodiment 1 of the present invention relates to.
Fig. 3 is the sketch of the structure of the hydrogen generation apparatus that relates to of expression embodiment 2 of the present invention.
Fig. 4 is the figure that the porous member that is provided with as the fixed support member on the hydrogen generation apparatus that relates to as embodiment 2 of the present invention is shown from the viewpoint of the direction of illumination of light.
Fig. 5 is the sketch of the structure of the hydrogen generation apparatus that relates to of expression embodiment 3 of the present invention.
Fig. 6 is the figure that the viewpoint from the direction of illumination of light is illustrated in the framework that is provided with as the fixed support member on the hydrogen generation apparatus that embodiment 3 of the present invention relates to.
Fig. 7 is the sketch of the structure of the hydrogen generation apparatus that relates to of expression embodiment 4 of the present invention.
Fig. 8 is in the hydrogen generation apparatus of representing to relate to as embodiment 4 of the present invention, the synoptic diagram of the band structure before a n type semiconductor layer of formation photocatalyst layer and the joint of the 2nd n type semiconductor layer.
Fig. 9 is the sketch of the structure of the hydrogen generation apparatus that relates to of expression embodiment 5 of the present invention.
Figure 10 is illustrated in the hydrogen generation apparatus that embodiment 5 of the present invention relates to, and constitutes the synoptic diagram of the band structure before the joint of a p type semiconductor layer and the 2nd p type semiconductor layer of photocatalyst layer.
Figure 11 is the sketch of the structure of the hydrogen generation apparatus that relates to of expression embodiment 6 of the present invention.
Figure 12 is the sketch of the structure of the hydrogen generation apparatus representing to use in an embodiment.
Figure 13 is the sketch that is illustrated in the structure of the hydrogen generation apparatus that uses in the comparative example.
Embodiment
Below, with reference to accompanying drawing embodiment of the present invention is at length described.Need to prove that following embodiment is merely an example, the present invention is not limited to following embodiment.And, in following embodiment,, omit the multiple explanation sometimes to same member mark prosign.
(embodiment 1)
Use Fig. 1 and Fig. 2 that the hydrogen generation apparatus of embodiment 1 of the present invention is described.Fig. 1 is the sketch of structure of the hydrogen generation apparatus of this embodiment of expression.Fig. 2 is the figure that is illustrated in first thrust that is provided with as the fixed support member on the hydrogen generation apparatus from the viewpoint of the direction of illumination of light.
The hydrogen generation apparatus 100 of this embodiment possesses transparency carrier 1, be configured in photocatalyst electrode 4, antipole 8 on the transparency carrier 1, be arranged between photocatalyst electrode 4 and the antipole 8 and contain the electrolyte layer of water, said electrolyte layer is separated into the partition member 6 of first electrolyte layer 5 and second electrolyte layer 7.First electrolyte layer 5 joins with photocatalyst electrode 4.Second electrolyte layer 7 joins with antipole 8.
In this embodiment, antipole 8 is configured on the back substrate 9.Back substrate 9 and transparency carrier 1 arranged opposite.Need to prove that " arranged opposite " here means the configuration that faces with each other of transparency carrier 1 and back substrate 9.Thereby, the structure that does not dispose only for transparency carrier 1 and back substrate 9 almost parallel ground due to that kind shown in Figure 1.That is, the configuration as long as transparency carrier 1 and back substrate 9 face with each other each other can be not parallel.And in Fig. 1, transparency carrier 1 has roughly the same size with back substrate 9.Yet transparency carrier 1 need not have identical size with back substrate 9, can have mutually different size and shape yet.
Direct of travel along the light that shines to hydrogen generation apparatus 100 describes; In hydrogen generation apparatus 100, dispose transparency carrier 1, transparency conducting layer 2, photocatalyst layer 3, first electrolyte layer 5, partition member 6, second electrolyte layer 7, antipole 8 and back substrate 9 in order from this side of irradiates light.That is, the mode faced across electrolyte layer with the surface of the surface of photocatalyst layer 3 and antipole 8 of photocatalyst electrode 4 and antipole 8 disposes.Need to prove, as long as the surface of photocatalyst layer 3 and antipole 8 is faced across electrolyte layer each other.Thereby, the structure that does not dispose only for surperficial almost parallel ground due to the surface of the photocatalyst layer 3 of that kind shown in Figure 1 and antipole 8.That is, as long as photocatalyst layer 3 is faced configuration mutually with antipole 8, surface each other can not be parallel to each other.And, in Fig. 1, show the structure that photocatalyst layer 3 and antipole 8 have roughly the same size.Yet photocatalyst layer 3 need not have identical size with antipole 8, can have mutually different size and shape yet.
Transparency conducting layer 2 is electrically connected via lead 10 with antipole 8 each other.Need to prove, transparency conducting layer 2 and lead 10 and antipole 8 and the electric connection point of lead 10 be insulated respectively that thing 11 covers in case with the contacting of electrolyte layer.
Hydrogen generation apparatus 100 passes through to photocatalyst layer 3 irradiates lights and with the water decomposition in the electrolyte layer to produce oxygen and hydrogen.In this embodiment, of the back, photocatalyst layer 3 uses the n N-type semiconductorN.Therefore, on the surface of photocatalyst layer 3, produce oxygen 24, and on the surface of antipole 8, produce hydrogen 25.On hydrogen generation apparatus 100, be provided with and be used for gas conveying end that the gas that produces in the inside of electrolyte layer is taken out.Be connected with the first gas conveying end 14 that gas that the inside at first electrolyte layer 5 is produced takes out at first electrolyte layer 5 that joins with photocatalyst layer 3.Be connected with at second electrolyte layer 7 that joins with antipole 8 and be used for the second gas conveying end 15 that the gas that the inside at second electrolyte layer 7 produces is taken out.In this embodiment, the first gas conveying end 14 constitutes the oxygen conveying end, and the second gas conveying end 15 constitutes the hydrogen conveying end.The first gas conveying end 14 and the second gas conveying end 15 are connected with the top of first electrolyte layer 5 and second electrolyte layer 7 respectively with the mode that connects housing 13.Need to prove, in Fig. 1,23 expression sealing members.
Next, each structure to hydrogen generation apparatus 100 describes particularly.
Transparency conducting layer 2 uses peripheral wavelength that the light that supplies visible regions and then expectation comprise the visible region at interior light transmission and material with electroconductibility.As the material of transparency conducting layer 2, tin indium oxide of having given an example (ITO) and fluorine-doped tin oxide (FTO).Thus, the light of the visible region of irradiation (and then the peripheral wavelength that preferably comprises the visible region is at interior light) arrives photocatalyst layer 3.
Photocatalyst layer 3 is formed by the n N-type semiconductorN.Photocatalyst layer 3 need be energized water of decomposition through rayed.Therefore, be that hydrionic standard electrode potential is below the 0V and the band edge energy level of valence band is that the standard oxidation potential of water is that semi-conductor more than the 1.23V forms preferably by the band edge energy level of conduction band.As such semi-conductor, use a kind of in titanium, tungsten, iron, copper, tantalum, gallium and the indium effectively or contain multiple element oxide compound, oxynitride and nitride, in above-mentioned materials, be added with alkalimetal ion or alkaline-earth metal ionic material, supported materials such as iron, copper, silver, gold or platinum at metallic surface.Particularly support the material of iron, copper, silver, gold or platinum etc. because superpotential is little and preferred at metallic surface.And, also use the stacked film that is bonded with each other and forms through the film that will to be the film that constitutes of the material below the hydrionic standard electrode potential 0V by the band edge energy level of conduction band constitute as the material more than the standard oxidation potential 1.23V of water with band edge energy level by valence band effectively.As an example, use for example WO effectively
3/ ITO/Si stacked film etc.
The thickness of photocatalyst layer 3 is preferably below the 100 μ m, so that can move well to face (with the interface of the first electrolyte layer 5) efficient of opposition side in the hole that the light entrance face side produces.In addition, owing to need absorb incident light fully, so the thickness of photocatalyst layer 3 is preferably more than the 0.2 μ m.
Need to prove that in this embodiment, photocatalyst layer 3 has used the n N-type semiconductorN, but also can use the p N-type semiconductorN.In this case, constitute the hydrogen generation apparatus that produces oxygen from the surface generation hydrogen of photocatalyst layer 3 and from the surface of antipole 8.
Constitute the electrolytic solution of first electrolyte layer 5 and second electrolyte layer 7 so long as contain the electrolytic solution of water and get final product, can also can be alkalescence for acidity.The thickness of first electrolyte layer 5 and second electrolyte layer 7 is preferred respectively in the scope of 2～10mm.Thus, carry out moving and diffusion of proton fully.And, through first electrolyte layer 5 and second electrolyte layer 7 are formed such thickness, also help to reduce the whole weight of hydrogen generation apparatus thus, therefore also preferred from the intensity aspect of mechanics.
On hydrogen generation apparatus 100, also be provided with the first jut 12a and the second jut 12b as the fixed support member that the position of partition member 6 is fixed and partition member 6 is supported.The fixed support member is used for partition member 6 is fixed and supporting, separates the arranged spaced of regulation with the surface with the surface of partition member 6 and photocatalyst layer 3 and antipole 8.That is, on whole of partition member 6, remain the surface of photocatalyst layer 3 and the interval of partition member 6 and the surface of antipole 8 and the interval of partition member 6 the same through the fixed support member.Need to prove that the interval of the interval of the surface of photocatalyst layer 3 and partition member 6 and the surface of antipole 8 and partition member 6 is not special to be limited.For example, two differ widely at interval and also can.As an example of such structure, the partition member 6 of having given an example is made up of the such softish material of Nafion (registered trademark), and is configured in and the surface of photocatalyst layer 3 or the very approaching such structure in position in surface of antipole 8.Need to prove that in this case, under the effect of the gas that produces on the surface with the approaching photocatalyst layer 3 (or antipole 8) of partition member 6, deflections take place partition member 6.Between the surface of partition member 6 and photocatalyst layer 3 (or antipole 8), form first electrolyte layer 5 (or second electrolyte layer 7) through the deflection of this partition member 6.Thereby there is not any problem in photocatalyst layer 3 (or antipole 8) with contacting of electrolytic solution.Yet if a side electrode is extremely narrow with the interval of partition member 6, the bubble of existence generation is attached in this interval and the collection and confinement of gases situation of difficult that becomes.Therefore, preferably partition member 6 is set with the roughly the same mode in two intervals.The fixed support member can use the fixed support member self not deform, and having to be such obdurability of not deflection and the material with insulativity with partition member 6 supportings.Given an example plastics, pottery, the covered metal of insulation etc.In addition, the fixed support member need be to have do not hindering under the situation about contacting of partition member 6 and electrolytic solution efficient to carry out ion moves so sufficient gap between first electrolyte layer 5 and second electrolyte layer 7 via partition member 6 structure well.
The first jut 12a is arranged on the surface of photocatalyst layer 3.The second jut 12b is arranged on the surface of antipole 8.As shown in Figure 2, when the viewpoint of the direction of illumination of light was observed the first jut 12a, the first jut 12a disposed a plurality of on the surface of partition member 6 equably.The second jut 12b be separately positioned on and the first jut 12a between clip partition member 6 and with the position that position consistency is set of the first jut 12a.That is, from observing with the direction of the Surface Vertical of partition member 6, the first jut 12a and the second jut 12b are configured on the overlapped position.Preferably confirm surface-area via the mode that moves of partition member 6 by photocatalyst layer 3, antipole 8 and the partition member 6 of the first jut 12a and second jut 12b covering with the lip-deep oxygen formation reaction that does not hinder photocatalyst layer 3, the lip-deep hydrogen formation reaction and the ion of antipole 8.The surface-area of the surface-area of the photocatalyst layer 3 that is covered by the first jut 12a and the second jut 12b, the surface-area of antipole 8 and partition member 6 is preferably for example below 10%, more preferably below 2% of whole area on said each surface respectively.Thus, even the first jut 12a and the second jut 12b are set, electrolytic solution is contacted fully with the surface of photocatalyst layer 3, the surface of antipole 8 and the surface of partition member 6.Therefore, can not hinder the lip-deep oxygen formation reaction of photocatalyst layer 3, the lip-deep hydrogen formation reaction and ion the moving of antipole 8 via partition member 6.
Next, the action to hydrogen generation apparatus 100 describes.
In hydrogen generation apparatus 100, the light that has seen through transparency carrier 1 and transparency conducting layer 2 is to photocatalyst layer 3 incidents.Through the light stimulus of photocatalyst layer 3, in photocatalyst layer 3, produce electronics in the conduction band, and produce the hole at valence band.The hole that produce this moment is to the surface of photocatalyst layer 3 (with the interface of first electrolyte layer 5) side shifting.Thus, water molecules is oxidized and produce oxygen (reactions formula (1)) on the surface of photocatalyst layer 3.On the other hand, electronics moves to transparency conducting layer 2.The electronics that moves to transparency conducting layer 2 via lead 10 to antipole 8 side shiftings.The electronics that moves in the inside of antipole 8 and arrived the surface (with the interface of second electrolyte layer 7) of antipole 8 reacts (reactions formula (2)) with the proton that supplies to the near surface of antipole 8, and produces hydrogen.The structure that the surface that hydrogen generation apparatus 100 constitutes photocatalyst layer 3 and the surface of antipole 8 are faced across electrolyte layer mutually.Therefore, all the lacking on the whole of the distance between the surface of the surface of photocatalyst layer 3 and antipole 8 on two surfaces than existing structure.Thus, can carry out proton fully and reach diffusion to the moving of surface of the antipole 8 that produces the hydrogen formation reaction.Consequently, even the hydrogen formation reaction is carried out,, therefore can suppress to carry out the reduction of reaction efficiency together with reaction because efficient is supplied with proton to the near surface of antipole 8 well.Oxygen that generates and hydrogen extract from the first gas conveying end 14 and the second gas conveying end 15 respectively.Along with the carrying out of water decomposition reaction, ion moving between first electrolyte layer 5 and second electrolyte layer 7 carried out via partition member 6.
4h
++2H
2O→O
2↑+4H
+ (1)
4e
-+4H
+→2H
2↑ (2)
Existing hydrogen generation apparatus is for to photocatalyst layer efficient irradiates light and constitute the structure of photocatalyst layer towards the rayed side well.With respect to this, the hydrogen generation apparatus 100 of this embodiment has the structure that photocatalyst layer 3 is faced across electrolyte layer and with antipole 8 mutually.In such structure, the light of decaying through transparency carrier 1 and transparency conducting layer 2 shines to photocatalyst layer 3.Thereby, think that the illumination efficiency this point of hydrogen generation apparatus 100 Dan Congguang of this embodiment is preferred unlike existing hydrogen generation apparatus.And in hydrogen generation apparatus 100, in photocatalyst layer 3, the face that produces the oxygen formation reaction is different with the plane of incidence of light.Therefore, the hole that produces through light stimulus must move to the surface of opposition side in photocatalyst layer 3 inside.From above-mentioned reason, anticipation photocatalyst layer 3 is that the hydrogen formation efficiency does not have so high structure across electrolyte layer and with structure that antipole 8 is faced mutually at a glance.Yet opposite with this anticipation, hydrogen generation apparatus 100 can realize fully that proton reaches diffusion to the moving of surface of the antipole 8 that generates the position as hydrogen, can further improve the hydrogen formation efficiency than existing hydrogen generation apparatus.
And, in hydrogen generation apparatus 100, second electrolyte layer 7 that electrolyte layer separates into first electrolyte layer 5 that joins with photocatalyst layer 3, joins with antipole 8 through partition member 6.Though partition member 6 sees through the ionogen in the electrolyte layer, be suppressed at seeing through of the hydrogen that produces in the electrolyte layer and oxygen.The oxygen that can the surface at photocatalyst layer 3 be produced thus, easily separates with the hydrogen that the surface at antipole 8 produces.
In addition, hydrogen generation apparatus 100 can will have the parts of transparency conducting layer 2 and photocatalyst layer 3, be formed with parts, partition member 6 integrated the assembling of antipole 8 on the substrate 9 overleaf through utilizing housing 13 in transparency carrier 1 laminated.Like this, hydrogen generation apparatus 100 has than the easy assembling of existing hydrogen generation apparatus and reduces the such advantage of parts number of packages.
(embodiment 2)
Use Fig. 3 and Fig. 4 that the hydrogen generation apparatus of embodiment 2 of the present invention is described.Fig. 3 is the sketch of structure of the hydrogen generation apparatus of this embodiment of expression.Fig. 4 is the figure that is illustrated in the porous member that is provided with as the fixed support member on the hydrogen generation apparatus from the viewpoint of the direction of illumination of light.
The hydrogen generation apparatus 200 of this embodiment has the structure identical with the hydrogen generation apparatus of embodiment 1 100 except the different this point of the shape of fixed support member.Therefore, only the porous member 16 that is provided with as the fixed support member is described at this.
Dispose the porous member 16 that constitutes by insulating material on the surface of first electrolyte layer, 5 sides of the partition member 6 in hydrogen generation apparatus 200.Porous member 16 engages with partition member 6, and is fixed on the housing 13.Through such structure, porous member 16 can support with the stationkeeping of partition member 6 and to partition member 6.Need to prove, in Fig. 4, for the ease of the structure that porous member 16 overlaps with partition member 6 is shown with understanding, and with the expression of staggering of the position of porous member 16 and partition member 6.Yet in this embodiment, when the direction of illumination of light was observed, porous member 16 disposed with the mode of partition member 6 with location overlap.
In hydrogen generation apparatus 200, in Fig. 3, be provided with porous member 16 in first electrolyte layer, 5 sides of partition member 6, but the allocation position of porous member 16 is not limited thereto.Porous member 16 can be configured in arbitrary side's of partition member 6 single face side, also can be configured in the two sides side.Thus, can remain the same with the interval of photocatalyst layer 3 and the interval of partition member 6 and antipole 8 on the whole at the face of partition member 6 partition member 6.
The illustrated fixed support member of porous member 16 and embodiment 1 is identical, can be by having the function that electrolytic solution is seen through fully, and have and can partition member 6 supportings be formed for the such obdurability of not deflection and material with insulativity.For example, porous tile, ceramic honeycomb body, foamed ceramic and porous matter plastics etc.The voidage of preferred porous member 16 for example is 50～90%, with carry out fully ion via partition member 6 mobile between first electrolyte layer 5 and second electrolyte layer 7.
Because the situation of the hydrogen generation apparatus 100 that the action of hydrogen generation apparatus 200 and embodiment 1 are illustrated is identical, therefore in this omission explanation.
According to hydrogen generation apparatus 200, can obtain the effect identical with the hydrogen generation apparatus of embodiment 1 100.
(embodiment 3)
Use Fig. 5 and Fig. 6 that the hydrogen generation apparatus of embodiment 3 of the present invention is described.Fig. 5 is the sketch of structure of the hydrogen generation apparatus of this embodiment of expression.Fig. 6 is the figure that is illustrated in the framework that is provided with as the fixed support member on the hydrogen generation apparatus from the viewpoint of the direction of illumination of light.
The hydrogen generation apparatus 300 of this embodiment has the structure identical with the hydrogen generation apparatus of embodiment 1 100 except the shape difference of fixed support member.Therefore, only the framework 17 that is provided with as the fixed support member is described at this.
Be provided with the framework 17 that constitutes by insulating material on the surface of first electrolyte layer, 5 sides of the partition member 6 in hydrogen generation apparatus 300.Framework 17 engages with partition member 6, and is fixed on the housing 13.Through such structure, framework 17 can fix and partition member 6 is supported the position of partition member 6.Need to prove, as shown in Figure 6, in this embodiment, the shape of framework 17 is formed reticulation, but be not limited thereto.Framework 17 is not so long as hinder ion to get final product via the shape that moves of partition member 6, can be shape arbitrarily.For example, if can the surface-area of the partition member 6 that is covered by framework 17 be made as partition member 6 below 10% of whole area, be preferably below 2%, then the setting of framework 17 can be moved ionic hardly and impacted.
In hydrogen generation apparatus 300, in Fig. 5, in first electrolyte layer, 5 sides of partition member 6 framework 17 is set, but the allocation position of framework 17 is not limited thereto.Framework 17 can be configured in arbitrary side's of partition member 6 single face side, also can be configured in the two sides side.Thus, can remain the same with the interval of photocatalyst layer 3 and the interval of partition member 6 and antipole 8 on the whole at the face of partition member 6 partition member 6.
The illustrated fixed support member of framework 17 and embodiment 1 is identical, can be by having the function that electrolytic solution is seen through fully, and have and can partition member 6 supportings be formed for the such obdurability of not deflection and material with insulativity.Given an example plastics, pottery, the covered metal of insulation etc.
Because the situation of the hydrogen generation apparatus 100 that the action of hydrogen generation apparatus 300 and embodiment 1 are illustrated is identical, therefore in this omission explanation.
According to hydrogen generation apparatus 300, can obtain the effect identical with the hydrogen generation apparatus of embodiment 1 100.
(embodiment 4)
Use Fig. 7 and Fig. 8 that the hydrogen generation apparatus of embodiment 4 of the present invention is described.Fig. 7 is the sketch of structure of the hydrogen generation apparatus of this embodiment of expression.Fig. 8 is illustrated in the hydrogen generation apparatus of this embodiment, the synoptic diagram of the band structure before a n type semiconductor layer of formation photocatalyst layer and the joint of the 2nd n type semiconductor layer.
The hydrogen generation apparatus 400 of this embodiment has the structure identical with the hydrogen generation apparatus of embodiment 1 100 except photocatalyst layer has the double-layer structure this point.Therefore, only the structure of photocatalyst layer is described at this.
The photocatalyst layer of the hydrogen generation apparatus 400 in this embodiment is made up of a n type semiconductor layer 18 that disposes in order from this side of irradiates light and the 2nd n type semiconductor layer 19.As shown in Figure 8, be benchmark with the vacuum level, the band edge energy level (E of conduction band in the 2nd n type semiconductor layer 19 and valence band
CB2, E
VB2) respectively than the band edge energy level (E of conduction band in the n type semiconductor layer 18 and valence band
CB1, E
VB1) big.And, be benchmark with the vacuum level, the fermi limit (E of a n type semiconductor layer 18
FB1) than the fermi limit (E of the 2nd n type semiconductor layer 19
FB2) big.
When a n type semiconductor layer 18 that will have such relation and the 2nd n type semiconductor layer 19 are bonded with each other, on the junction surface of a n type semiconductor layer 18 and the 2nd n type semiconductor layer 19 so that the consistent mode of fermi limit each other moves current carrier.Thus, produce the bending of band edge.Band edge energy level (the E of the band edge energy level of the conduction band of the 2nd n type semiconductor layer 19 and valence band
CB2, E
VB2) respectively than the band edge energy level of the conduction band of a n type semiconductor layer 18 and the band edge energy level (E of valence band
CB1, E
VB1) big.And, the fermi limit (E of a n type semiconductor layer 18
FB1) than the fermi limit (E of the 2nd n type semiconductor layer 19
FB2) big.Through above-mentioned relation, on the junction surface of a n type semiconductor layer 18 and the 2nd n type semiconductor layer 19, do not produce Schottky barrier.
Generate electronics and holes through light stimulus in a n type semiconductor layer 18 inside.The electronics that generates moves to the conduction band of a n type semiconductor layer 18.The hole that generates moves to the surface (interface of the 2nd n type semiconductor layer 19 and first electrolyte layer 5) of the 2nd n type semiconductor layer 19 on valence band along the bending of band edge.Thereby electronics and hole are not hindered by Schottky barrier can, and by chargeseparated effectively.Thus, electronics that produce in a n type semiconductor layer 18 inside through light stimulus and hole be bonded probability step-down once more.Hole efficient moves to the surface of the 2nd n type semiconductor layer 19 well, so the quantum yield of the hydrogen formation reaction that causes of rayed is able to further raising.
As a n type semiconductor layer 18, preferably use for example titanium oxide, strontium titanate, niobium oxides, zinc oxide and potassium tantalate etc.As the 2nd n type semiconductor layer 19, preferably use for example Cadmium Sulfide, tantalum nitride oxide and tantalum nitride etc.As concrete combination, preference uses titanium oxide (anatase titanium dioxide) and the 2nd n type semiconductor layer 19 use Cadmium Sulfides like a n type semiconductor layer 18.
Because the situation of the hydrogen generation apparatus 100 that the action of hydrogen generation apparatus 400 and embodiment 1 are illustrated is identical, therefore in this omission explanation.
According to hydrogen generation apparatus 400, can obtain the effect identical with the hydrogen generation apparatus of embodiment 1 100.Wherein, as stated, in hydrogen generation apparatus 400, photocatalyst layer is made up of two-layer n type semiconductor layer.Through this structure, hydrogen generation apparatus 400 is compared with the hydrogen generation apparatus 100 of embodiment 1, can promote electronics and the chargeseparated in hole in the photocatalyst layer.Thereby, obtain the further lip-deep oxygen formation reaction and the such effect of antipole 8 lip-deep hydrogen formation reaction of acceleration photocatalyst layer.
Need to prove, in this embodiment, the photocatalyst layer 3 with the hydrogen generation apparatus 100 of embodiment 1 is illustrated by the form that two-layer n type semiconductor layer constitutes.Yet, can be suitable for the structure of this embodiment too to the photocatalyst layer 3 of the hydrogen generation apparatus 300 of the hydrogen generation apparatus 200 of embodiment 2 and embodiment 3.
(embodiment 5)
Use Fig. 9 and Figure 10 that the hydrogen generation apparatus of embodiment 5 of the present invention is described.Fig. 9 is the sketch of structure of the hydrogen generation apparatus of this embodiment of expression.Figure 10 is illustrated in the hydrogen generation apparatus of this embodiment, the synoptic diagram of the band structure before a p type semiconductor layer of formation photocatalyst layer and the joint of the 2nd p type semiconductor layer.
The hydrogen generation apparatus 500 of this embodiment has the structure identical with the hydrogen generation apparatus of embodiment 1 100 except photocatalyst layer has the double-layer structure this point.Therefore, only the structure of photocatalyst layer is described at this.
The photocatalyst layer of the hydrogen generation apparatus 500 in this embodiment is made up of a p type semiconductor layer 20 that disposes in order from this side of irradiates light and the 2nd p type semiconductor layer 21.In this embodiment, because photocatalyst layer is formed by the p N-type semiconductorN, therefore different with embodiment 1～4 is, produces the hydrogen formation reaction and in antipole 8 generation oxygen formation reaction at photocatalyst layer.Thereby the first gas conveying end 14 that is connected with first electrolyte layer 5 constitutes the hydrogen conveying end, and the second gas conveying end 15 that is connected with second electrolyte layer 7 constitutes the oxygen conveying end.
Shown in figure 10, be benchmark with the vacuum level, the band edge energy level (E of conduction band in the 2nd p type semiconductor layer 21 and valence band
CB2, E
VB2) respectively than the band edge energy level (E of conduction band in the p type semiconductor layer 20 and valence band
CB1, E
VB1) little.And, be benchmark with the vacuum level, the fermi limit (E of a p type semiconductor layer 20
FB1) than the fermi limit (E of the 2nd p type semiconductor layer 21
FB2) little.
When a p type semiconductor layer 20 that will have such relation and the 2nd p type semiconductor layer 21 are bonded with each other, on the junction surface of a p type semiconductor layer 20 and the 2nd p type semiconductor layer 21 so that the consistent mode of fermi limit each other makes carrier flow.Thus, produce the bending of band edge.Band edge energy level (the E of the band edge energy level of the conduction band of the 2nd p type semiconductor layer 21 and valence band
CB2, E
VB2) respectively than the band edge energy level of the conduction band of a p type semiconductor layer 20 and the band edge energy level (E of valence band
CB1, E
VB1) little.And, the fermi limit (E of a p type semiconductor layer 20
FB1) than the fermi limit (E of the 2nd p type semiconductor layer 21
FB2) little.According to above-mentioned relation, on the junction surface of a p type semiconductor layer 20 and the 2nd p type semiconductor layer 21, do not produce Schottky barrier.
Generate electronics and holes through light stimulus in a p type semiconductor layer 20 inside.Move to the valence band of a n type semiconductor layer 20 in the hole that generates.The electronics that generates moves to the surface (interface of the 2nd p type semiconductor layer 21 and first electrolyte layer 5) of the 2nd p type semiconductor layer 21 on the conduction band along the bending of band edge.Thereby electronics and hole are not hindered by Schottky barrier, and by chargeseparated effectively.Thus, make in the inner electronics that generate of a p type semiconductor layer 20 and hole bonded probability step-down once more through light stimulus.Because electronic efficiency moves to the surface of the 2nd p type semiconductor layer 21 well, so the quantum yield of the hydrogen formation reaction that causes of rayed is able to further raising.
As a p type semiconductor layer 20, preferably use for example Red copper oxide etc.As the 2nd p type semiconductor layer 21, preferably use for example cupric sulfide indium, copper indium gallium selenide etc.As concrete combination, preference uses Red copper oxide and the 2nd p N-type semiconductorN 21 to use the cupric sulfide indium like a p type semiconductor layer 20.
Because the situation of the hydrogen generation apparatus 100 that the action of hydrogen generation apparatus 500 and embodiment 1 are illustrated is identical, therefore in this omission explanation.
According to hydrogen generation apparatus 500, can obtain the effect identical with the hydrogen generation apparatus of embodiment 1 100.Wherein, as stated, in hydrogen generation apparatus 500, photocatalyst layer is made up of two-layer p type semiconductor layer.Through this structure, hydrogen generation apparatus 500 is compared with the hydrogen generation apparatus 100 of embodiment 1, can promote electronics and the chargeseparated in hole in the photocatalyst layer.Thereby the lip-deep hydrogen formation reaction of photocatalyst layer and the lip-deep oxygen formation reaction of antipole 8 are able to further acceleration.
Need to prove, in this embodiment, the photocatalyst layer 3 with the hydrogen generation apparatus 100 of embodiment 1 is illustrated by the form that two-layer p type semiconductor layer constitutes.Yet, can be suitable for the structure of this embodiment too to the photocatalyst layer 3 of the hydrogen generation apparatus 300 of the hydrogen generation apparatus 200 of embodiment 2 and embodiment 3.
(embodiment 6)
Use Figure 11 that the hydrogen generation apparatus of embodiment 6 of the present invention is described.Figure 11 is the sketch of structure of the hydrogen generation apparatus of this embodiment of expression.
In the hydrogen generation apparatus 600 of this embodiment, on lead 10, be provided with the supply unit 22 that is used to apply bias voltage as the access path that transparency conducting layer 2 is electrically connected with antipole 8.Need to prove that hydrogen generation apparatus 600 has the structure identical with the hydrogen generation apparatus of embodiment 1 100 except that this point.In hydrogen generation apparatus 600, at light-struck bias voltage that applies simultaneously.Thus, further quicken the lip-deep oxygen formation reaction of photocatalyst layer 3 and the lip-deep hydrogen formation reaction of antipole 8.
Need to prove, in this embodiment, the hydrogen generation apparatus 100 of embodiment 1 has been suitable for the structure that applies bias voltage.Yet, all can be suitable for the structure of this embodiment equally to embodiment 2～5 illustrated all hydrogen generation apparatus.
Embodiment
(embodiment)
Embodiments of the invention are specifically described.As embodiment, used hydrogen generation apparatus shown in Figure 12 700.This hydrogen generation apparatus 700 is except being provided with fixed support member (the first jut 12a and the second jut 12b) this point, has the structure identical with the illustrated hydrogen generation apparatus of embodiment 6 600.Wherein, on lead 10, connect the rheometer 26 that is used to measure the photoelectric current that obtains.
The mode that the parts that make at the parts that are provided with transparency conducting layer 2 and photocatalyst layer 3 on the transparency carrier 1 and be provided with antipole 8 overleaf on the substrate 9 are faced across partition member 6 between with photocatalyst layer 3 and antipole 8 is opposed.Above-mentioned parts are kept by housing 13 integratedly.Distance between the surface of the surface of photocatalyst layer 3 and antipole 8 is 15mm.The surface of partition member 6 and photocatalyst layer 3 and the surface of antipole 8 be at a distance of about equally distance, and dispose with above-mentioned surperficial almost parallel ground.The oxygen that partition member 6 uses the proton that can make in the electrolyte layer to see through and be suppressed to produce in the electrolyte layer and the ion-exchange membrane that sees through (" Nafion " (E.I.Du Pont Company's system)) of hydrogen.Partition member 6 has and roughly the same shape of transparency carrier 1 and back substrate 9 and identical size.
Utilize lead 10 to be electrically connected transparency conducting layer 2 and antipole 8, and on access path, be provided with the supply unit 22 that is used to apply bias voltage.And, the first gas conveying end 14 and the second gas conveying end 15 are set with the mode that connects housing 13.Electrolytic solution uses the aqueous sodium hydroxide solution of 0.1mol/L.
The hydrogen generation apparatus 700 of as above such present embodiment that is made is come irradiates light from the xenon lamp of transparency carrier 1 side working strength 100W.At this moment, use supply unit 22 to apply the bias voltage of 0.5V simultaneously.Mobile photoelectric current between transparency conducting layer 2 and antipole 8 is measured, be 1.57mA.
(comparative example)
As comparative example, make hydrogen generation apparatus 800 shown in Figure 13.In this hydrogen generation apparatus 800, the photocatalyst electrode 4 that is made up of transparency conducting layer 2 and photocatalyst layer 3 is arranged on the surface of partition member 6 with transparency conducting layer 2 and antipole 8 opposed modes.And, be provided with the gap (vertical 10mm * horizontal 30mm) that the proton that is used for electrolysis liquid moves in the bottom of photocatalyst electrode 4.
Except the configuration of photocatalyst electrode 4 and the shape, likewise make the hydrogen generation apparatus 800 of comparative example with the hydrogen generation apparatus 700 of embodiment.During with the condition irradiates light identical with embodiment, the mobile photoelectric current is 0.57mA between transparency conducting layer 2 and antipole 8 to this hydrogen generation apparatus 800.
As stated, according to making the opposed hydrogen generation apparatus of the present invention of photocatalyst layer and antipole across electrolyte layer, and photocatalyst layer is compared towards the existing hydrogen generation apparatus of rayed side configuration, flow through high photoelectric current.That is, according to hydrogen generation apparatus of the present invention, the efficient of hydrogen formation reaction is improved.
Industrial applicibility
Hydrogen generation apparatus of the present invention can improve the quantum yield of the hydrogen formation reaction that rayed causes, therefore can be suitable for work is supplied with hydrogen supply source etc. from hydrogen to fuel cell.
Claims (10)
1. hydrogen generation apparatus, it possesses:
Transparency carrier;
The photocatalyst electrode, it is formed by the photocatalyst layer that is configured in the transparency conducting layer on the said transparency carrier and be configured on the said transparency conducting layer;
Antipole, it is electrically connected with said transparency conducting layer;
Electrolyte layer, it is arranged between said photocatalyst electrode and the said antipole and contains water;
Partition member, it is separated into first electrolyte layer that joins with said photocatalyst electrode and second electrolyte layer that joins with said antipole with said electrolyte layer;
The first gas conveying end, it is connected with said first electrolyte layer, is used to take out oxygen or the hydrogen that produces in the inside of said first electrolyte layer;
The second gas conveying end, it is connected with said second electrolyte layer, is used to take out hydrogen or the oxygen that produces in the inside of said second electrolyte layer,
Said photocatalyst electrode disposes with the mode that the surface of said antipole is faced mutually with the surface of said antipole with said photocatalyst layer,
Said partition member can make the ionogen in the said electrolyte layer see through and the hydrogen and the oxygen that suppress in the said electrolyte layer see through.
2. hydrogen generation apparatus according to claim 1, wherein,
Also possess housing, this housing keeps said transparency carrier, said photocatalyst electrode, said electrolyte layer, said partition member and said antipole as one.
3. hydrogen generation apparatus according to claim 1, wherein,
Also possess the fixed support member that the position of said partition member is fixed and said partition member is supported,
The interval that said fixed support member separates regulation with the surface and the surface of said antipole of said partition member and said photocatalyst layer and the mode of configured in parallel fix said partition member and are supported.
4. hydrogen generation apparatus according to claim 3, wherein,
Said fixed support member is lip-deep second thrust that is arranged on lip-deep first thrust of said photocatalyst layer and is arranged on said antipole,
Said first thrust and said second thrust are clipped in the middle said partition member and are arranged on each other on the consistent location.
5. hydrogen generation apparatus according to claim 3, wherein,
Also possess housing, this housing keeps said transparency carrier, said photocatalyst electrode, said electrolyte layer, said partition member and said antipole as one,
Said fixed support member is arranged on between said photocatalyst layer and the said partition member and the arbitrary at least side's who selects between said antipole and the said partition member position, and by the porous member of said housing maintenance.
6. hydrogen generation apparatus according to claim 3, wherein,
Also possess housing, this housing keeps said transparency carrier, said photocatalyst electrode, said electrolyte layer, said partition member and said antipole as one,
Said fixed support member is arranged on between said photocatalyst layer and the said partition member and the arbitrary at least side's who selects between said antipole and the said partition member position, and by the framework of said housing maintenance.
7. hydrogen generation apparatus according to claim 1, wherein,
Being shaped as flat board, having the dull and stereotyped of communicating pores or being provided with the flat board of otch of said antipole.
8. hydrogen generation apparatus according to claim 1, wherein,
Said photocatalyst layer is formed by a n type semiconductor layer that disposes in order from said transparency conducting layer side and the 2nd n type semiconductor layer,
With the vacuum level is benchmark,
(I) the band edge energy level of conduction band in said the 2nd n type semiconductor layer and valence band is respectively greater than the conduction band in the said n type semiconductor layer and the band edge energy level of valence band, and,
(II) fermi limit of a said n type semiconductor layer is greater than the fermi limit of said the 2nd n type semiconductor layer.
9. hydrogen generation apparatus according to claim 1, wherein,
Said photocatalyst layer is formed by a p type semiconductor layer that disposes in order from said transparency conducting layer side and the 2nd p type semiconductor layer,
With the vacuum level is benchmark,
(I) the band edge energy level of conduction band in said the 2nd p type semiconductor layer and valence band is respectively less than the conduction band in the said p type semiconductor layer and the band edge energy level of valence band, and,
(II) fermi limit of a said p type semiconductor layer is less than the fermi limit of said the 2nd p type semiconductor layer.
10. hydrogen generation apparatus according to claim 1, wherein,
Also possess with the supply unit that is used to apply bias voltage that is provided with on said transparency conducting layer and the access path that said antipole is electrically connected.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010-012216 | 2010-01-22 | ||
| JP2010012216 | 2010-01-22 | ||
| PCT/JP2011/000269 WO2011089904A1 (en) | 2010-01-22 | 2011-01-19 | Hydrogen generation device |
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| Publication Number | Publication Date |
|---|---|
| CN102713010A true CN102713010A (en) | 2012-10-03 |
| CN102713010B CN102713010B (en) | 2015-10-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201180006506.8A Expired - Fee Related CN102713010B (en) | 2010-01-22 | 2011-01-19 | Hydrogen generation apparatus |
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| Country | Link |
|---|---|
| US (1) | US8734625B2 (en) |
| EP (1) | EP2527495B1 (en) |
| JP (1) | JP5628840B2 (en) |
| CN (1) | CN102713010B (en) |
| WO (1) | WO2011089904A1 (en) |
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Also Published As
| Publication number | Publication date |
|---|---|
| EP2527495A1 (en) | 2012-11-28 |
| JPWO2011089904A1 (en) | 2013-05-23 |
| EP2527495A4 (en) | 2015-01-14 |
| WO2011089904A1 (en) | 2011-07-28 |
| US20120285823A1 (en) | 2012-11-15 |
| EP2527495B1 (en) | 2017-05-31 |
| CN102713010B (en) | 2015-10-07 |
| JP5628840B2 (en) | 2014-11-19 |
| US8734625B2 (en) | 2014-05-27 |
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